Wegen der zunehmenden Menge an LIBS-Daten von der Marsoberfläche sowie deren speziellen Herausforderungen bei der Analyse untersucht diese Arbeit, wie die Modellierung und Simulation von solchen LIBS-Spektren genutzt werden kann. Das Ziel ist es, Einblicke in die Eigenschaften von LIBS-Plasmen auf dem Mars zu erhalten und Modelle zu entwickeln, die bei der Analyse von realen Missionsdaten helfen können. Die Modellierung basiert sich auf einem stationären Plasma im lokalen thermischen Gleichgewicht (LTE). Das Plasma wird dabei in eine Reihe homogener Zonen unterteilt und Spektren werden mit dem Strahlungstransfer entlang einer eindimensionalen Sichtlinie durch diese Plasmazonen simuliert. Die Ergebnisse dieser Arbeit zeigen, dass auf LTE basierende Modelle gut auf LIBS-Spektren angewendet werden können, die unter Marsbedingungen gemessen wurden. Für zeitaufgelöste Daten kann die Anpassung eines Zwei-Zonen-Modells verwendet werden, um Einblicke in das Plasma zu erhalten und um die Elementkonzentrationen mit einer höheren Genauigkeit zu bestimmen, als es mit der Saha-Boltzmann-Methode möglich wäre. Allerdings sollten Nicht-Gleichgewichtseffekte in den frühesten und spätesten Phasen der Plasmalebensdauer berücksichtigt werden. Für zeitlich integrierte Spektren, wie sie bei aktuellen Marsmissionen gemessen werden, sind Anpassungen durch ein Zwei-Zonen-Modell aufgrund von zu langen Rechenzeiten nicht durchführbar. Stattdessen kann durch die Methode der spektralen Entmischung eine Überlagerung von Spektren unterschiedlicher Temperaturen und Dichten verwendet werden. Diese Methode ermöglicht keine direkten quantitativen Bestimmungen der Elementkonzentrationen, ist aber ein hervorragendes Werkzeug, um einen Überblick über die große Menge an Informationen zu erhalten, die in den Spektren enthalten sind. / Motivated by existing challenges in analysing LIBS spectra and the increasing quantity of Martian LIBS data, this thesis investigates the modelling and simulation of LIBS spectra for the application to LIBS data in Martian atmospheric conditions. This is done with the aim of providing insights into the characteristics of Martian LIBS plasmas as well as developing tools to assist the analysis of real mission data. The modelling of LIBS spectra is based on a stationary plasma in local thermal equilibrium (LTE). The plasma is then divided into a series of homogeneous zones and spectra are simulated using radiative transfer along a one-dimensional line-of-sight through the plasma zones. The results of this thesis show that spectral modelling based on LTE can be well applied to LIBS data in Martian atmospheric conditions. For time-resolved data, fits of a two-zone plasma model can be used to obtain insights into the plasma as well as improved concentration estimates compared to the Saha-Boltzmann plot method. However, attention to non-equilibrium effects should be given at the earliest and latest stages of the plasma lifetime. For time-integrated spectra, i.e. real mission data, fits of the two-zone model are not feasible due to too long computation times. Instead, a superposition of spectra of different temperatures and densities, i.e. the spectral unmixing method, can be used. Although not directly allowing for quantitative concentration estimates, the method is a great tool to overview the large amount of information contained in the spectra.

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<p dir="ltr">Emission and absorption spectroscopy diagnostics are useful for providing non-invasive,<br>quantitative measurements of various gas properties in combustion environments, including<br>temperature and species concentrations. These measurements become even more useful<br>when they are applied with high spatial and temporal resolution. This dissertation describes<br>several ways that both emission and absorption diagnostics were advanced through leveraging<br>improvements in mid-IR camera and laser technology and through refining the use of existing<br>techniques.<br>A literature review is provided for both laser absorption and emission spectroscopy. Previous advancements in spatially resolved techniques are explained. The fundamental equations<br>of spectroscopic diagnostics are reviewed, starting from statistical mechanics.<br>A spectrally-resolved emission imaging diagnostic is presented. This diagnostic provided<br>1-dimensional measurements of gas temperature and relative mole fraction of CO₂ and HCl<br>in flames. An imaging spectrometer and a high-speed mid-infrared camera were used to<br>provide 1D measurements of CO₂and HCl emission spectra with a spectral resolution of<br>0.46 cm^-1 at rates up to 2 kHz. Measurements were acquired in HMX and AP-HTPB flames<br>burning in air at 1 atm. This diagnostic was applied to characterize how the path-integrated<br>gas temperature of HMX flames varies in time and with distance above the burning surface.<br>Additionally, Abel inversion with Tikhonov regularization was applied to determine the radial<br>distribution of temperature and relative concentration of CO₂ and HCl within the core of<br>AP-HTPB flames.<br>Next, a similar emission imaging diagnostic is presented which uses spectrally-resolved<br>measurements of emission spectra at visible wavelengths, unlike the mid-infrared measure-<br>ments in the rest of this dissertation. This diagnostic provided 1D temperature measure-<br>ments of aluminum oxide (AlO), an intermediate product of aluminum combustion. While<br>this author created the AlO diagnostic, these measurements were performed alongside a CO<br>absorption diagnostic used by a different researcher to compare the flame bath gas (via CO)<br>and the region immediately around aluminum particles (via AlO) when varying forms of<br>aluminum powder were used in a propellant. This comparison allows analysis of the burning regime of aluminum particles. Evidence was found that nano-aluminum particles burn in<br>the kinetically controlled combustion regime, while micron-aluminum particles burn in the<br>diffusion-controlled regime.<br>Multi-spectral emission imaging of hypergolic ignition of ammonia borane (AB) is then<br>presented. Three high-speed cameras with multiple optical filters were used to capture<br>infrared and visible wavelength videos of four individual species during AB ignition: BO,<br>BO₂, HBO₂, and the B-H stretch mode of AB were imaged. The ignition process was<br>observed to act in two steps: gas evolution and then propagation of a premixed flame. The<br>evolution of the species and flame front revealed that boranes may continue to complete<br>combustion to a further degree than other boron fuels. This author performed the infrared<br>camera imaging and also ran infrared spectrograph measurements to confirm which species<br>were viewed through the optical filters.<br>Next, a scanned-wavelength direct-absorption diagnostic for directly measuring NH₃ in<br>high-temperature combustion environments is presented. A quantum cascade laser (QCL)<br>was scanned at 5 kHz over multiple NH₃ transitions between 959.9 cm⁻¹ and 960.3 cm⁻¹ to<br>measure path-integrated NH₃ temperature and mole fraction. Many NH₃ transitions overlap<br>with high-temperature water lines at commonly used diagnostic frequencies, severely limiting<br>those diagnostics’ capabilities in water-rich, high-temperature environments that are typical<br>of combustion applications. The optical frequencies used in this diagnostic are insensitive<br>to water absorption and thus remedy this issue. This diagnostic was demonstrated within<br>the flame of ammonia borane. AB-based fuels were burned in ambient air and translated<br>vertically to effectively scan the measurement line-of-sight vertically through the flame. Ad-<br>ditionally, flames of these fuels were characterized at a stationary height in an opposed-flow<br>burner (OFB) under O₂ flow.<br>The final chapter presents scanned-wavelength direct-absorption measurements of path-<br>integrated temperature and CO mole fraction in opposed-flow diffusion flames of hydroxyl-<br>terminated polybutadiene (HTPB). HTPB strands were held in an opposed-flow burner<br>under an opposed flow of O2 or 50/50 O₂/N₂ to create quasi-steady and quasi-1D diffusion<br>flames above the fuel strand. The opposed-flow burner was translated vertically to effectively<br>scan the measurement line-of-sight vertically through the flame. A quantum-cascade laser (QCL) was scanned across the P(2,20), P(0,31), and P(3,14) absorption transitions in CO’s<br>fundamental vibration bands near 2008 cm⁻¹ at 10 kHz to determine the path-integrated<br>temperature and CO mole fraction. The laser beam was passed through sapphire rods<br>held close to the flame edge to bypass the flame boundary and provide a well defined path<br>length for mole fraction measurements. The measured profiles and fuel regression rates<br>were compared to predictions produced by a steady opposed-flow 1D diffusion flame model<br>produced by researchers at the Army Research Lab. The model was generated with chemical<br>kinetics mechanisms employing two different assumptions for the nascent gaseous product of<br>HTPB pyrolysis: C₄H₆ or C₂₀H₃₂. It was found that the C₂₀H₃₂ model produced temperature<br>and CO profiles along with regression rates that agreed more closely with the measured<br>results.<br></p>

The purpose of this dissertation is to — on occasion very literally — shine a light on processes that occur in non-thermal plasmas containing CO2, mostly for CO2 conversion. In particular, the focus lies on the transient behaviour of these discharges: how do these systems evolve over time before they settle in a (non-thermal) equilibrium. In addition to that, it analyses trends in the field of plasma-catalytic CO2 conversion as a whole to evaluate the current state-of-the-art, but also presents a new platform for the community to contribute and collaborate on, to facilitate cross-comparison between disparate experiments. The first part consists of experiments performed on: (a) an atmospheric pressure nanosecond repetitively pulsed (NRP) discharge for CO2 conversion, and (b) a test bed system for a remote CCP plasma source for plasma-enhanced atomic layer deposition (PE-ALD) of trimethylaluminium (TMA). The common theme in these experiments is a focus on the application of time-resolved, in situ diagnostics to study transient behaviour in the systems under investigation. The main diagnostics employed for such measurements are optical emission spectroscopy (OES) and laser induced fluorescence (LIF), which can provide complementary results when used in conjunction. In particular, this work presents the following results: A study of the evolution of emission from an NRP discharge (using OES), establishing both electron densities (by Stark broadening of atomic oxygen and carbon lines) and gas temperatures (by the N2 second positive system) as the discharge evolves from a breakdown phase to a spark phase. It furthermore explores the changes to these properties when operating in burst mode, where a subsequent pulse experiences a memory effect from the preceding one, which has been shown to be conducive to efficient conversion in literature. A study into the effect on energy efficiency of CO2 conversion by alternating the power modulation in an NRP discharge. Crucially, using CET-LIF (collisional energy transfer LIF) and OES it is shown that while power deposition to the discharge occurs in the order of 100 ns in the discharge, CO2 dissociation occurs on a timescale beyond a microsecond. This indicates that instead of direct electron impact, molecular-excitation kinetics play an important role under these conditions for CO2 dissociation. By shortening the time between pulses in a burst (down to 33 us in the work), these mechanisms can be further enhanced, by prolonging the quasi-‘metastable’ state of the system. The application of LIF in a PE-ALD process plasma along with OES, where diffusion profiles were measured close to the substrate surface with local time-resolved measurements of the OH ground state density. These indicate that the investigated surface reactions finish on a timescale of 100 ms, faster than would be indicated by OES which effectively measures emission from the bulk plasma after diffusion of reaction products away from the surface. The second part of this work is an open access database on plasma(-catalytic) CO2 conversion that is instrumental in identifying and verifying trends in experimental data, but also stresses the importance of rigorous reporting of essential parameters in literature. The approach in literature is diverse: some studies focus more on a mechanistic understanding of the fundamental processes, whilst others already focus on process tailoring and optimization for industrial applications. Trends observed in earlier review papers are observed as well and can now be trivially reproduced. The database platform (https://db.co2pioneer.eu) is put forward as a new tool for the community to easily cross-compare and contextualize experimental outcomes and strongly encourages new contributions. Based on the 196 papers included at the time of publication, a number of observations and recommendations can already be made. Chief among those is a clear and present need in the field for a more fundamental understanding of plasma-catalysis interaction, to develop techniques and criteria that are properly suited to test the synergy of both, rather than relying on methods from e.g. traditional thermal-catalysis. Also in this instance, local, time-resolved diagnostics may play a key role, but their implementation will be challenging.

The concept of plasma flow control is a relatively new idea based on using atmospheric plasma placed near the edge of an air foil to reduce boundary layer losses. As with any new concept, it is important to be able to quantify theoretical assumptions with known experimental results for validation. Currently there are a variety of experiments being done to better understand plasma flow control, but one particular experiment is through the use of multi-physics modeling of dielectric barrier discharge actuators. The research in this thesis uses optical measurement techniques to validate computational models of flow control actuators being done concurrently at Virginia Tech. The primary focus of this work is to design, build and test plasma actuators in order to determine the plasma characteristics relating to electron temperatures and densities. Using optical measurement techniques such as plasma spectroscopy, measured electron temperatures and densities to compare with theoretical calculations of plasma flow control under a variety of flow conditions. This thesis covers a background of plasma physics, optical measurement techniques, and the designing of the plasma actuator setups used in measuring atmospheric plasmas. / Master of Science

L'objectif de cette thèse est de fournir une meilleure compréhension des différents phénomènes physiques liés aux microplasmas/microdécharges. Pour cela, des matrices de microréacteurs sur silicium ont été étudiées. De nombreuses configurations ont été construites de manière à analyser l’influence de chaque paramètre physique sur le fonctionnement de ces dispositifs. Le présent travail porte sur l'élaboration et la caractérisation de dispositifs micro-décharge à base de silicium. Dans ce travail de thèse, les régimes de courant continu (DC) et de courant alternatif (AC) sont étudiés en utilisant des configurations de décharges différentes. Pour la fabrication de ces réacteurs, nous sommes partis de wafers de Silicium que nous avons structurés et traités en salle blanche. La technologie de fabrication utilisée est compatible avec les méthodes de fabrication de dispositifs CMOS. Les microréacteurs sont constitués d’électrodes de nickel et de silicium séparés par une couche diélectrique de SiO2 de 6 μm d’épaisseur. L’épaisseur du diélectrique est ici beaucoup plus faible que celle des microréacteurs étudiés jusqu’à présent. Les dispositifs sont constitués de cavités de 25 à 150 microns de diamètre. Les essais de microdécharge ont été effectués dans des gaz inertes à une pression comprise entre 100 et 1000 Torrs. Nous avons d’abord étudié les phénomènes d’allumage et d’extinction à partir de microdispositifs monocavité en alumine. Puis, nous avons étudié le fonctionnement en DC/AC de microréacteurs en silicium comportant un nombre de cavité compris entre 1 et1024. Les caractéristiques des microdécharges ont été étudiées grâce à des mesures électriques, des mesures de spectroscopie d'émission optique (OES), de spectroscopie d’absorption à diode laser (DLAS) et de spectroscopie d'émission optique résolue en temps (PROES). Ces différents diagnostics nous ont permis de mettre en évidence les phénomènes d’allumage, d’extinction, d’instabilité et les mécanismes de défaillance de nos microdispositifs. Ce travail de thèse a permis de tester les performances et les limites technologiques des matrices de microdécharges sur silicium. Une attention particulière a été portée sur leur durée de vie. / The objective of this thesis is to provide a better understanding of various physical phenomena related to microplasmas/microdischarges. For this purpose, arrays of microreactors on silicon were studied. Different array configurations were fabricated to analyse the influence of each parameter on the physical operation of these devices. The present work focuses on the development and characterisation of micro-discharge devices based on silicon. In this thesis, direct current (DC) and alternating current (AC) regimes are studied using different discharge configurations. For the fabrication of these reactors, Silicon wafers are structured and processed in a cleanroom. Fabrication technology used is compatible with the CMOS technology. The microreactors are fabricated with nickel and silicon electrodes, separated by a dielectric layer of SiO2 with a thickness of 6 μm. The thickness of the dielectric is much lower here than the microreactors studied so far. The devices consist of cavities with 25 to 150 μm in diameter. Experiments of the microdischarges are performed in inert gases at a pressure between 100 and 1000 Torr. We first studied the phenomena of ignition and extinction for the microdevices based on alumina. Then, we studied the microreactors based on silicon containing 1 to 1024 cavities under DC and AC regimes. Characteristics of microdischarges were studied by electrical measurements, measurements of optical emission spectroscopy (OES), laser diode absorption spectroscopy (DLAS) and phase resolved optical emission spectroscopy (PROES). These diagnostics allowed us to investigate the phenomena of ignition, extinction, instability and failure mechanisms of the microplasma devices. This thesis work allowed testing the performance and technological limitations of the silicon based microdischarge arrays. Particular attention was paid to their life time.

The objective of this thesis is to provide a better understanding of various physical phenomena related to microplasmas/microdischarges. For this purpose, arrays of microreactors on silicon were studied. Different array configurations were fabricated to analyse the influence of each parameter on the physical operation of these devices. The present work focuses on the development and characterisation of micro-discharge devices based on silicon. In this thesis, direct current (DC) and alternating current (AC) regimes are studied using different discharge configurations. For the fabrication of these reactors, Silicon wafers are structured and processed in a cleanroom. Fabrication technology used is compatible with the CMOS technology. The microreactors are fabricated with nickel and silicon electrodes, separated by a dielectric layer of SiO2 with a thickness of 6 μm. The thickness of the dielectric is much lower here than the microreactors studied so far. The devices consist of cavities with 25 to 150 μm in diameter. Experiments of the microdischarges are performed in inert gases at a pressure between 100 and 1000 Torr. We first studied the phenomena of ignition and extinction for the microdevices based on alumina. Then, we studied the microreactors based on silicon containing 1 to 1024 cavities under DC and AC regimes. Characteristics of microdischarges were studied by electrical measurements, measurements of optical emission spectroscopy (OES), laser diode absorption spectroscopy (DLAS) and phase resolved optical emission spectroscopy (PROES). These diagnostics allowed us to investigate the phenomena of ignition, extinction, instability and failure mechanisms of the microplasma devices. This thesis work allowed testing the performance and technological limitations of the silicon based microdischarge arrays. Particular attention was paid to their life time.

A qualidade dos efluentes líquidos do Pólo Industrial de Belford Roxo e das águas do Rio Sarapuí foram avaliadas por meio de ensaios de toxicidade aguda com Daphnia similis, Ceríodaphnia dúbia e Danio rerio e ensaios de toxicidade crônica com Ceriodaphnia dúbia e Selenastrum capricornutum. Em associação ao monitoramento ecotoxicológico, foram realizados os procedimentos de Avaliação e Identificação da Toxicidade - AIT (Toxicity Identification Evaluation - TIE) os quais possibilitaram a identificação dos agentes tóxicos para as duas matrizes. Para o efluente, foi identificado o íon cloreto como principal agente tóxico, complementado por efeitos aditivos de metais, amônia e sulfeto. As águas do Rio Sarapuí apresentam os nutrientes fósforo e nitrogênio como principais agentes tóxicos, com toxicidade aditiva de metais, amônia e sulfeto. Embora a Estimativa de Impactos Ambientais a partir dos dados de toxicidade do efluente sugira impactos mínimos por parte do lançamento de efluentes do Pólo no compartimento água superficial, a qualidade das águas desse rio já apresenta por si só um impedimento à manutenção da vida aquática. O constante lançamento de esgoto não tratado compromete a qualidade das águas do rio Sarapuí, culminando num quadro de completa degradação devido ao aumento da concentração de nutrientes e matéria orgânica, que acaba por inviabilizar o correto equilíbrio desse ecossistema e suas interações ecológicas naturais. / The quality of Belford Roxo Industrial Plant effluent and water from Sarapuí River were evaluated with Daphnia similis, Ceriodaphnia dubia and Danio rerio acute and chronic toxicity tests. In association with the ecotoxicological monitoring, the Toxicity Identification Evaluation procedure were performed and the identification of the toxic compounds was possible. The Chloride ion was identified as the major toxic compound in the effluent with additional effects of Metals, Ammonium and Sulfide. For the Sarapuí River, the compounds of Phosphorus and Nitrogen were identified as the major toxic compounds with addictive effects of Metals, Ammonium and Sulfide. Although the environmental impact estimation based on the effluent toxicity suggests a minor impact on the water quality of Sarapuí River, this was already sufficiently contaminated to make impracticable the establishment of an aquatic community. The constant discharge of untreated sludge promotes the eutrophication of this water body and makes impossible the equilibrium of this ecosystem.